US4760127A - Process for the preparation of polyarylene sulphide with monohalogeno aromatic compound and mono mercapto compound - Google Patents

Process for the preparation of polyarylene sulphide with monohalogeno aromatic compound and mono mercapto compound Download PDF

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US4760127A
US4760127A US06/893,601 US89360186A US4760127A US 4760127 A US4760127 A US 4760127A US 89360186 A US89360186 A US 89360186A US 4760127 A US4760127 A US 4760127A
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mol
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alkali metal
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Wolfgang Ebert
Karsten Idel
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/025—Preparatory processes
    • C08G75/0254—Preparatory processes using metal sulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0231—Polyarylenethioethers containing chain-terminating or chain-branching agents

Definitions

  • the invention relates to a process for the preparation of high molecular weight, optionally branched polyarylene sulphides from alkali metal sulphides and dihalogenoaromatics in a polar solvent in the presence of 0.05 to 5.0 mol %, preferably 0.1 to 2.5 mol %, of in each case a monohalogen and a monomercapto compound.
  • the resulting polyarylene sulphides of defined melt viscosities are distinguished by a high stability of the melt and low corrosion.
  • Polyarylene sulphides and their preparation are known (for example U.S. Pat. Nos. 2,513,188 and 3,117,620).
  • alkali metal carboxylates DE-AS (German Published Specification) No. 2,453,749)
  • lithium halides or alkali metal carboxylates DE-OS (German Published Specification) No. 2,623,362)
  • lithium chloride or lithium carboxylate DE-OS (German Published Specification) No. 2,623,363)
  • alkali metal carbonates in combination with alkali metal carboxylates U.S. Pat. No. 4,038,259
  • lithium acetate DE-OS (German Published Specification) No. 2,623,333
  • tri-alkali metal phosphates DE-OS (German Published Specification) No.
  • the invention therefore relates to a process for the preparation of optionally branched polyarylene sulphides from
  • the radicals R 1 and R 2 is identical or different and can be hydrogen, C 1 -C 4 -alkyl, C 5 -C 10 -cycloalkyl, C 6 -C 10 -aryl, C 7 -C 10 -alkylaryl or C 7 -C 14 -arylalkyl, it being possible for two radicals R 1 in the ortho-position relative to one another to be linked to form an aromatic ring or a heterocyclic ring containing up to three heteroatoms, such as N, O or S, and one radical R 1 always being other than hydrogen, and
  • Ar is an aromatic C 6 -C 14 radical or a heterocyclic radical with 5 to 14 ring atoms, it being possible for up to 3 ring C atoms to be replaced by heteroatoms, such as N, O or S,
  • n the number 3 or 4
  • an alkali metal sulphide preferably sodium sulphide or potassium sulpide or a mixture thereof, for example in the form of their hydrates or aqueous mixtures, if appropriate together with small amounts of alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, and 0 to 50 mol % of an alkali metal bisulphide, preferably sodium bisulphide or potassium bisulphide, or a mixture thereof, it being possible for the molar ratio of (a+b):c to be in the range from 0.75:1 to 1.25:1, and
  • reaction accelerators such as alkali metal carboxylates, alkali metal phosphates, alkali metal phosphonates, alkali metal fluorides or alkali metal alkylsulphonates, or in the presence of N,N-dialkylcarboxylic acid amides, lactams, anhydrides and esters of carboxylic acids, characterized in that monohalogenoaromatics of the formula IV
  • reaction mixture are added to the reaction mixture in amounts of 0.05 to 5.0 mol %, preferably 0.1 to 2.5 mol %,
  • W is a replaceable group selected from the group comprising halogen, such as Cl, Br and I, mesylate and tosylate, preferably Cl or Br,
  • A is an aliphatic, aromatic or heterocyclic radical with 6 to 30 C atoms, for example ##STR3## wherein the radicals R 3 independently of one another denote C 1 -C 8 -alkyl; C 7 -C 19 -alkaryl/aralkyl, C 3 -C 6 -cycloalkyl or hydrogen and
  • Z represents C 1 -C 6 -alkylidene, C 3 -C 6 -cycloalkylidene, CO, --S--, --SO 2 --, O or a chemical single bond and
  • Y denotes O, NR 3 , S, SO 2 or CO, and furthermore
  • k, m and p are integers, and in particular
  • k represents the number 0, 1 or 2
  • n 0, 1, 2, or 3
  • p represents the number 0, 1, 2, 3, or 4
  • R has the meaning of R 3 ,
  • SW is a mercapto or mercaptide group, in which
  • A is an aliphatic, aromatic or heterocyclic radical with 1 to 30 C atoms, for example ##STR4## and Z, Y, k, m, p and R 3 have the meaning given in the case of formula IV.
  • the alkali metal sulphides are preferably employed in the form of their hydrates and aqueous mixtures or aqueous solutions. Dehydration can be partial, but is preferably carried out completely. The water present in the reaction mixture is distilled out of the batch. The distillation of the water can be carried out directly or with the aid of agents which form azeotropes, the dihalogenoaromatics preferably being employed as agents which form an azeotrope. For the dehydration, all the reaction partners can be mixed and dehydration of the entire mixture can be carried out.
  • the alkali metal sulphide can also be dehydrated separately with some of the reaction components or by itself.
  • the reaction partners are continuously brought together with the reaction accelerator or a mixture of reaction accelerators in the presence of the polar solvent, the water being simultaneously removed.
  • a reaction which starts can be controlled via the rates of metering. Longer residence times of the water can thus also be avoided.
  • the reaction can be carried out under normal pressure or under a low pressure of up to about 3 bar.
  • a higher pressure of up to 50 bar can be applied.
  • the reaction can be carried out continuously or discontinuously.
  • the reaction time can be varied within a wide range. It can be from 1 to 48 hours, preferably 1 to 18 hours.
  • the reaction temperatures are between 150° and 300° C., preferably between 170° and 280° C.
  • the mercapto compound V and the monohalogen compound IV can be added in various ways.
  • the monohalogen compound can initially be taken, whilst the mercapto compound is added at a particular point in the subsequent stirring period, or the reverse procedure can be followed.
  • the mercapto compound or the monohalogen compound can be initially taken whilst the other particular compound is metered in continuously during the reaction or post-condensation period; furthermore, both compounds can be metered in or added in portions at certain intervals of time in the reaction or subsequent stirring phase.
  • both defined compounds and also mixtures of various monohalogen compounds or mixtures of various mercapto compounds can be used.
  • the polyarylene sulphides prepared according to the invention are distinguished by defined melt viscosities which can be reproduced within a narrow range. This is of great importance inasmuch as polymer melts with different flow properties which must be adapted to suit the particular intended use must be established for processing the polyarylene sulphides.
  • melt viscosities are required for the production of films and fibres than for establishing injection moulding grades reinforced with glass fibres or glass fibres/mineral.
  • polyarylene sulphides prepared according to the invention are their high stability under exposure to heat. Only thus is it guaranteed that no further build-up or degradation which can lead to a complete change in the pattern of properties can occur during thermoplastic processing. The regenerated material can also be reused again after processing.
  • reaction mixture can be worked up and the polyarylene sulphides can be isolated in a known manner.
  • the polyarylene sulphide can be separated off directly from the reaction solution or, for example, after first adding water and/or dilute acids or organic solvents with a low solubility for polyarylene sulphides, by the customary procedures, for example by filtration or by centrifugation. After the polyarylene sulphide has been separated off, it is in general subsequently washed with water. Washing or extraction with other washing liquids, which can also be carried out in addition to or after this washing, is also possible.
  • the polyarylene sulphide can also be obtained, for example, by distilling off the solvent and subsequent washing, as described above.
  • the alkali metal sulphides can also be obtained, for example, from H 2 S and alkali metal hydroxides.
  • alkali metal hydroxide can additionally be metered in, depending on the amount of alkali metal bisulphide contained in the reaction solution as an impurity in the alkali metal sulphide. If appropriate, those compounds which split off or form alkali metal hydroxides under the reaction conditions can also be added, instead of the alkali metal hydroxides.
  • meta- and para-dihalogenoaromatics of the formula (I) and (II) can be employed.
  • the ratio of meta- to para-dihalogenoaromatics can be up to 30:70.
  • p-Dihalogenoaromatics are preferably used to obtain polyphenyl sulphides which can be processed as thermoplastics.
  • branched polyarylene sulphides are to be prepared, at least 0.05 mol % of a tri- or tetrahalogenoaromatic of the formula (III) should be employed.
  • dihalogenoaromatics of the formula (I) which are to be employed according to the invention are: p-dichlorobenzene, p-dibromobenzene, 1-chloro-4-bromobenzene, 1,3-dichlorobenzene, 1,3-dibromobenzene and 1-chloro-3-bromobenzene. They can be used by themselves or as a mixture with one another. 1,4-Dichlorobenzene and/or 1,4-dibromobenzene are particularly preferred.
  • dihalogenoaromatics of the formula (II) which are to be employed according to the invention are: 2,5-dichlorotoluene, 2,5-dichloroxylene, 1-ethyl-2,5-dichlorobenzene, 1-ethyl-2,5-dibromobenzene, 1-ethyl-2-bromo-5-chlorobenzene, 1,2,4,5-tetramethyl-3,6-dichlorobenzene, 1-cyclohexyl-2,5-dichlorobenzene, 1-phenyl-2,5-dichlorobenzene, 1-benzyl-2,4-dichlorobenzene, 1-phenyl-2,5-dibromobenzene, 1-p-tolyl-2,5-dichlorobenzene, 1-p-tolyl-2,5-dibromobenzene, 1-hexyl-2,5-dichlorobenzene, 2,4-dichlorotol
  • Examples of tri- or tetrahalogenoaromatics of the formula (III) which are to be employed according to the invention are: 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4-tribromobenzene, 1,3,5-trichloro-2,4,6-trimethylbenzene, 1,2,3-trichloronaphthalene, 1,2,4-trichloronaphthalene, 1,2,6-trichloronaphthalene, 2,3,4-trichlorotoluene, 2,3,6-trichlorotoluene, 1,2,3,4-tetrachloronaphthalene, 1,2,4,5-tetrachlorobenzene, 2,2'-4,4'-tetrachlorobiphenyl and 1,3,5-trichlorotriazine.
  • any polar solvent which guarantees a sufficient solubility of the organic and, if appropriate, inorganic reactants under the reaction conditions can be employed for the reaction.
  • N-Alkyllactams are preferably used.
  • N-Alkyllactams are those of amino acids with 3 to 11 C atoms, which can optionally carry substituents which are inert under the reaction conditions on the carbon skeleton.
  • N-alkyllactams which are used are: N-methylcaprolactam, N-ethylcaprolactam, N-isopropylcaprolactam, N-isobutylcaprolactam, N-propylcaprolactam, N-butylcaprolactam, N-cyclohexylcaprolactam, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-methyl-3,4,5-trimethyl-2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-2-piperidone, N-isobutyl-2-piperidone, N-
  • Examples of monohalogenoaromatics and heterocyclic compounds which can be employed according to the invention are 3-chlorodiphenyl, 4-chlorodiphenyl, 3-bromodiphenyl, 4-chlorodiphenyl, 2-chlorodiphenyl ether, 4-chlorodiphenyl ether, 2-bromodiphenyl ether, 4-bromodiphenyl ether, 2-chlorodiphenyl sulphide, 3-chlorodiphenyl sulphide, 4-chlorodiphenyl sulphide, 2-bromodiphenyl sulphide, 3-bromodiphenyl sulphide, 4-bromodiphenyl sulphide, 2-chlorodiphenyl sulphoxide, 4-chlorodiphenyl sulphoxide, 2-bromodiphenyl sulphoxide, 4-bromodiphenyl sulphoxide, 2-chlorodiphenyl sulphoxide, 3-chlorodiphenyl s
  • the reaction can additionally be carried out in the presence of customary reaction accelerators, such as, for example: alkali metal carboxylates (DE-AS (German Published Specification) No. 2,453,749), lithium halides or alakli metal carboxylates (DE-OS (German Published Specification) No. 2,623,362), lithium chloride or lithium carboxylate (DE-OS (German Published Specification) No. 2,623,363), alkali metal carbonates in combination with alkali metal carboxylates (U.S. Pat. No. 4,038,259), lithium acetate (DE-OS (German Published Specification) No. 2,623,333), tri-alkali metal phosphates (DE-OS (German Published Specification) No.
  • customary reaction accelerators such as, for example: alkali metal carboxylates (DE-AS (German Published Specification) No. 2,453,749), lithium halides or alakli metal carboxylates (DE-OS (German Published Specification) No. 2,623,362), lithium chloride
  • the polyarylene sulphides according to the invention can be mixed with other polymers, such as pigments and fillers--for example graphite, metallic powders, glass powder, quartz flour, glass fibres or carbon fibres--or the additives customary for polyarylene sulphides, for example customary stabilizers or mould release agents, can be added.
  • pigments and fillers for example graphite, metallic powders, glass powder, quartz flour, glass fibres or carbon fibres--or the additives customary for polyarylene sulphides, for example customary stabilizers or mould release agents, can be added.
  • melt flow properties of polyarylene sulphides are in general measured in accordance with ASTM 1238-70 at 316° C. using a 5 kg weight and are quoted in g/10 minutes.
  • the melt viscosity ⁇ m of the polymer melt has therefore been determined (in Pa ⁇ s) at 306° C. as a function of the shearing stress (in Pa) with the aid of an Instron rotation viscometer.
  • the melt viscosity can be determined in a very wide range from 10 -1 to 10 7 Pa ⁇ s in this manner.
  • the polymer is melted between a fixed plate and a rotatable cone and the torque of the cone is determined. From the torque, the angular viscosity and the apparatus data, the melt viscosity can be calculated as a function of the shearing stress.
  • the polyarylene sulphides according to the invention After isolation from the reaction mixture, the polyarylene sulphides according to the invention have melt viscosities between 1 and 5 ⁇ 10 3 , preferably 5 to 1 ⁇ 10 3 Pa ⁇ s. They can be processed in the customary manner. Films, fibres and, preferably, injection moulding compositions are thereby obtained. These can be used, for example, as automobile components, fittings, electrical components, for example switches, electronic boards, components and apparatuses which are resistant to chemicals and stable to weathering, such as pump housings and pump impellers, etching bath dishes, sealing rings, components of office machines and communication equipment and as domestic appliances, valves, ball bearing components, embedding compositions for electronic components and the like.
  • Polyarylene sulphides can be analyzed by chromatographic processes to obtain information on their molecular weight and molecular weight distribution.
  • HPLC high pressure liquid chromatography
  • GPC gel permeation chromatography
  • the customary solvents can be used as the solvent and mobile phase. These should dissolve the polymer sufficiently.
  • Suitable examples are 1-chloronaphthalene, diphenyl, N-methylpyrrolidone, N-cyclohexylpyrrolidone, N-methylpiperidone, N-methylcaprolactam, N-methyllaurinelactam, sulpholane, N,N'-dimethylimidazolidinone, N,N'-dimethylpiperazinone, hexamethylphosphoric acid triamide, 1-methyl-1-oxo-phospholane and mixtures thereof.
  • Absolute or relative calibrations can be carried out in the chromatographic analytical methods.
  • suitable calibration substances for relative are customary polymers, such as, for example, polystyrene, polyethylene, polyethylene terephthalate, polybutylene terephthalate, polyesters, such as purely aromatic polyesters, polycarbonate, polyamides, such as PA 6, PA 66 and PA 11, polysulphones or polyether-sulphones.
  • the chromatographic determination is carried out at a temperature from room temperature to 250° C.
  • Substances such as alkali metal halides, alkaline earth metal carboxylates and phosphonium or ammonium compounds can furthermore be added to the sample to be analysed to improve the measurement accuracy.
  • the reaction is kept under reflux for a further 4 hours and 1.76 g (0.25 mol %) of thiophenol in 50 ml of N-methylcaprolactam are then metered in. After a further reaction time of 3 hours, the PPS is precipitated in water, washed free from electrolyte and briefly extracted with an organic solvent. The dried p-polyphenylene sulphide has a melt viscosity of 41 Pa ⁇ s (measured at 10 2 Pa and 306° C.).
  • This example is as Example 2, but without 4-chlorodiphenyl sulphone and without thiophenol.
  • This polyphenylene sulphide can be processed only with difficulty in the presence of relatively large amounts of mineral fillers or glass fibres because of its reduced flowability.
  • Example 2 This example is as Example 2; however, the thiophenol is already metered in after 2 hours 30 minutes.
  • the p-polyphenylene sulphide obtained has a melt viscosity of 34 Pa ⁇ s (measured at 10 2 Pa and 306° C.).
  • Example 2 This example is as Example 2, but with methyloxophospholane as the solvent.
  • a p-polyphenylene sulphide with a melt viscosity of 37 Pa ⁇ s (measured at 10 2 Pa and 306° C.) is obtained.
  • This example is as Example 2; however, 2.66 g (0.25 mol %) of 2-mercaptobenzimidazole are taken and 8.08 g (0.5 mol %) of 4-chlorodiphenyl sulphone in 50 ml of N-methylcaprolactam are added after a subsequent stirring time of 2 hours.
  • the corrosion was determined by titration of acid gas emissions from the corresponding polyphenylene sulphide samples in a stream of air at 350° C. in 1 hour.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
US06/893,601 1985-08-17 1986-08-06 Process for the preparation of polyarylene sulphide with monohalogeno aromatic compound and mono mercapto compound Expired - Fee Related US4760127A (en)

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DE19853529501 DE3529501A1 (de) 1985-08-17 1985-08-17 Verfahren zur herstellung von hochmolekularen, gegebenenfalls verzweigten polyarylensulfiden
DE3529501 1985-08-17

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5175243A (en) * 1990-11-14 1992-12-29 Phillips Petroleum Company Process for preparing arylene sulfide polymers with halo benzene containing deactivating group
US5288848A (en) * 1985-08-17 1994-02-22 Bayer Aktiengesellschaft Process for preparation of high molecular weight, optionally branched polyarylene sulphides
US5296579A (en) * 1988-02-11 1994-03-22 Phillips Petroleum Company Arylene sulfide polymers
US5328980A (en) * 1992-12-03 1994-07-12 Phillips Petroleum Company Method of preparing poly(arylene sulfide) polymers, polymers and polymer blends

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3703550A1 (de) * 1987-02-06 1988-08-18 Bayer Ag Verfahren zur herstellung von polyarylensulfiden mit regelbaren schmelzviskositaeten
US4820800A (en) * 1988-02-25 1989-04-11 Phillips Petroleum Company Arylene sulfide polymers
DE3808496A1 (de) * 1988-03-15 1989-09-28 Bayer Ag Neue hochmolekulare, gegebenenfalls verzweigte co-polyarylensulfide, verfahren zu deren herstellung und deren verwendung
DE3808915A1 (de) * 1988-03-17 1989-10-05 Bayer Ag Benzoxazol- oder oxazolingruppen-haltige polyarylsulfide
DE3811451A1 (de) * 1988-04-06 1989-10-19 Bayer Ag Polyarylensulfide mit erniedrigter kristallisationstemperatur und verfahren zu deren herstellung
US4952671A (en) * 1988-07-15 1990-08-28 Eastman Kodak Company Terminated copoly(arylene sulfide)
DE4006397A1 (de) * 1989-05-17 1990-11-29 Bayer Ag Verfahren zur herstellung von mono- und multifilamenten sowie stapelfasern auf basis von polyarylensulfiden, sowie hochfeste polyarylensulfid-fasern
EP2115035B1 (en) 2007-01-04 2018-04-25 SK Chemicals Co., Ltd. Polyarylene sulfide resin with excellent luminosity and preparation method thereof

Citations (4)

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US3386950A (en) * 1965-08-31 1968-06-04 Phillips Petroleum Co Stabilized poly
US3870686A (en) * 1973-11-19 1975-03-11 Phillips Petroleum Co Arylene sulfide polymers
EP0053344A1 (en) * 1980-11-27 1982-06-09 Toray Industries, Inc. Stabilized polyphenylene sulfide and method for producing same
EP0100536A2 (en) * 1982-07-29 1984-02-15 Kureha Kagaku Kogyo Kabushiki Kaisha Process for producing aromatic sulfide polymers

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
US3386950A (en) * 1965-08-31 1968-06-04 Phillips Petroleum Co Stabilized poly
US3870686A (en) * 1973-11-19 1975-03-11 Phillips Petroleum Co Arylene sulfide polymers
EP0053344A1 (en) * 1980-11-27 1982-06-09 Toray Industries, Inc. Stabilized polyphenylene sulfide and method for producing same
EP0100536A2 (en) * 1982-07-29 1984-02-15 Kureha Kagaku Kogyo Kabushiki Kaisha Process for producing aromatic sulfide polymers

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5288848A (en) * 1985-08-17 1994-02-22 Bayer Aktiengesellschaft Process for preparation of high molecular weight, optionally branched polyarylene sulphides
US5296579A (en) * 1988-02-11 1994-03-22 Phillips Petroleum Company Arylene sulfide polymers
US5175243A (en) * 1990-11-14 1992-12-29 Phillips Petroleum Company Process for preparing arylene sulfide polymers with halo benzene containing deactivating group
US5328980A (en) * 1992-12-03 1994-07-12 Phillips Petroleum Company Method of preparing poly(arylene sulfide) polymers, polymers and polymer blends

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JPH0645689B2 (ja) 1994-06-15
DE3529501A1 (de) 1987-02-19
JPS6241226A (ja) 1987-02-23
DE3675853D1 (de) 1991-01-10
EP0214470B1 (de) 1990-11-28
EP0214470A1 (de) 1987-03-18

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